Stoichiometric Table Batch System

Stoichiometry set up of equations with A as basis

aA + bB cC + dD
specie initial

change

i = Nio/NAo
= (d/a) + (c/a) (b/a) - 1
remaining

NAo

NBo = NAo B

-(b/a)NAo X

NB = NAo[B (b/a)X]

NCo = NAo C

+(c/a)NAo X

NC = NAo[C +(c/a)X]

NDo = NAo D

+(d/a)NAo X

ND = NAo[D +(d/a)X]

NI = NAo I

NI = NAo I

NTo = NAo i

NT = NTo +NAoX

-NAo X

NA = NAo(1 X)

Stoichiometric Tables
Express table in terms of concentrations
Concentration (batch):

Ni
Ci =
V

Constant Volume Batch

V = V0

NA NA 0 (1 X )
=
= C A 0 (1 X )
CA =
V
V0
CB =

CC =

ND NA 0
c
c

+
X
=
C

+
X
C

A0
C
V
V0
a
a

ND NA 0
d
d
b
NB NA 0
b

=
=

+
=

+
C
X
C
X
=

X
=
C

D
D
A0
D
A0 B
a
V
V0
a
V
V0
a
a

Stoichiometric Tables
Elementary rate law substitution:
aA + bB cC + dD

a b C cCCDd

rA = k A C A CB
KC

NA NA 0 (1 X )
CA =
=
= C A 0 (1 X )
V
V0
CB =

CC =

ND NA 0
c
c

+
X
=
C

+
X
C

A0
C
V
V0
a
a

ND NA 0
d
d
NB NA 0
b
b

=
=

+
X
=
C

+
X
C
=

X
=
C

D
D
A0
D
A0 B
V
V0
a
a
V
V0
a
a

Stoichiometric Table Flow System

Stoichiometry set up of equations with A as basis

aA + bB cC + dD
specie initial

i = Fio/Fao= Cioo/Cao o= yio/yao

= (d/a) + (c/a) (b/a) - 1

change

remaining

FAo

FBo = FAo B

-(b/a)FAo X

FB = FAo[B (b/a)X]

FCo = FAo C

+(c/a)FAo X

FC = FAo[C +(c/a)X]

FDo = FAo D

+(d/a)FAo X

FD = FAo[D +(d/a)X]

FI = FAo I

-FAo X

FTo = FAo i
i

FA = FAo(1 X)

FI = FAo I
FT = FTo +FAoX

Stoichiometric Tables
Express table in terms of concentrations
concentration (liquid flow):

Fi
Ci =

constant volumetric flowrate

= 0

FA FA 0 (1 X )
CA = =
= C A 0 (1 X )

0
FB FA 0
b
b

CB = =
B X = C A 0 B X
a
a
0

Stoichiometric Tables
Express table in terms of concentrations
concentration for variable
volumetric gas flow:

Fi
Ci =

From compressibility factor EOS

FT T P0
= 0
FT 0 T0 P

T P
= 0 (1 + y A 0 X ) 0
T0 P

FA 0 T P0
= 0 1 +
X
FT 0 T0 P

T P0
= 0 (1 + X )
T0 P

Stoichiometric Tables
Express table in terms of concentrations
concentration for variable
volumetric gas flow:

Fi
Ci =

From compressibility factor EOS

T P0
= 0 (1 + X )
T0 P

FA 0 1 X T0 P
C A =

0 1 + X T P0

FA
CA =

1 X T0 P
CA = CA0

1 + X T P0

Stoichiometric Tables
Express table in terms of concentrations
concentration for variable
volumetric gas flow:

Fi
Ci =

From compressibility factor EOS

T P0
= 0 (1 + X )
T0 P

B [b a]X T0 P
CB = C A 0

+

1
X

T P0

FA
CA =

1 X T0 P
CA = CA0

1 + X T P0

Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.

Set up a stoichiometric table, assuming the feed

is in stoichiometric proportions and comprised
only of reactants. Use chlorine as the basis for
calculation.

Example
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

Component

Symbol

Initial

Change

Out

Cl2

-X

1-X

CH4

0.5

-0.5X

0.5(1-X)

CH2Cl2

+0.5X

0.5X

HCl

+X

Total

1.5

1.5

Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.

Calculate .

= y Ao
=0

d c b
= + 1
a a a
= 2 +12 1
=0

Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.

Evaluate rA in terms of conversion of chlorine,

the specific reaction rate, and the initial chlorine
concentration.

Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.

0.2 dm6/(smol2) 3rd Order (assume elementary)

rA = kC2A CB

Need stoichiometry for CA & CB

Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.
System is gas phase until Pc = 400 mm Hg. Need to find
conversion at which CH2Cl2 condenses

n1P1 = n2P2
(1.5)(760) = (0.5 X')(400)
X' = 1.58

C A = C Ao (1 X A )
1
CB = C Ao (1 X A )
2

Therefore, CH2Cl2 does not condense in this system

Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.
Substitute stoichiometry into rate law

rA = kC2A CB

= k[C Ao (1 X A )]2 [(C Ao 2)(1 X A )]

k 3
= C Ao (1 X A )3
2

Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.

What is the concentration of chlorine at X = 60% ?

C Ao = y Ao

P
RT

1
1 atm
=
1.5 (0.082L atm mol K )(298.2K )
= 0.027mol dm3

C A = C Ao (1 X A )

C A = 0.027mol dm3 (1 0.6 )

= 0.011 = mol dm3

Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.

What is the rate of reaction at X = 60%?

k
rA = C3Ao (1 X A )3
2
0.2 dm6 s mol2
3 3
=
0.027mol dm (1 0.6 )3
2
= 1.26 10 7 mol dm3 s

Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.

What is the activation energy if the frequency

factor is 2 x 1012 dm6/smol2 ?

k = Ae E RT

Arrhenius Equation

0.2 dm6 s mol2 = 2 1012 dm6 s mol2 e E (8.314 J molK )(298.2K )

E = 74212 J mol

Example
The following elementary gas-phase reaction takes place in a constantpressure isothermal vessel (1 atm, 25C):
h
CH4 (g) + 2Cl2 (g)
CH2Cl2 (g ,l) + 2HCl(g)

k = 0.2 dm6/(smol2) at 25C (estimated)

CH2Cl2: Pvap = 400 mm Hg (53 kPa) at 25C.

What is the specific reaction rate at 100C ?

k100
1
E 1
= exp

= 410
k 25
R 373.2 298.2
k100 = k 25 410 = 81.95 dm6 s mol2

Arrhenius
Equation

Example (with phase change)

The gas-phase reaction between chlorine and methane to
form carbon tetrachloride and hydrochloric acid is to be
carried out at 75C and at 950 kPa in a continuous-flow
reactor.

4Cl2 + CH4 CCl4 + 4HCl

The vapor pressure of carbon tetrachloride at 75C is 95 kPa.

Volumetric flow rate is 0.4 dm3/s
Set up a stoichiometric table for this reaction with phase change. Calculate
the conversion of methane at which condensation begins.
Plot the concentrations and molar flow rates of each species as well as the
total molar flow rate as a function of conversion for a stoichiometric feed.

Example (with phase change)

4Cl2 + CH4 CCl4 + 4HCl
T = 75C = 348 K
P = 950 kPa = 9.39 atm
PV ,CCl4 = 95 kPa = 0.94 atm
PV 95
y CCl4 ,e = =
= 0.1
P 950

Example (with phase change)

Stoichiometry set up of equations with CH4 as basis

4Cl2 + CH4 CCl4 + 4HCl

change

remaining
(PD<PV) before
condensation

remaining
(PD=PV) after
condensation

specie

initial

A - CH4

FAo

-FAo X

FA = FAo(1 X)

FAo(1 X)

B - Cl2

4 FAo

-4FAo X

FB = 4FAo[1 X]

4FAo[1 X]

C - HCl4

+4FAo X

FC = 4FAoX

4FAoX

D(g) - CCl4 (g)

+FAo X

FD = FAoX

0.1 FT

FT = 5FAo

FT = FAo(5-X)

FTo = 5FAo

(0.9)

Example (with phase change)

When condensation begins,

FT = F'T
5 Xc
5FAo = FAo
0.9
X c = 0.5
Therefore, condensation begins at 50% conversion

Example (with phase change)

Before Condensation
Total concentration is constant

= y Ao

=0

=0

Po
gmol

T
=

P
=
0
C T = C To =
= 0.329
RTo
L
1
0.329
gmol
C Ao = C To =
= 0.0658
5
5
L
gmol
L
gmol
0.4 = 0.02631
FAo = C Ao o = 0.0658
s
L
s
Fi
Fi
Fi
=
Ci = =
o (1 + X ) o

Example (with phase change)

Expressing stoichiometric table column remaining (PD<PV) before
condensation in terms of
Fi
Ci =
o
specie

Fi

Ci

A - CH4

FAo(1 X)

CAo(1 X)

B - Cl2

4FAo[1 X]

4CAo(1 X)

C - HCl4

4FAoX

4CAoX

D(g) - CCl4 (g)

FAoX

CAoX

total

5FAo

5CAoX

Example (with phase change)

After Condensation

FT '
= o
FTo
FAo (5 X )
= o
5FAo (0.9 )
5X
= o

4.5

Fi Fi 5 X
Ci = =

o 4.5

Example (with phase change)

Expressing stoichiometric table column remaining (PD=PV) after
condensation in terms of

Fi 5 X
Ci =

o 4.5

Fi

Ci

A - CH4

FAo(1 X)

CAo(1 X) (4.5)/(5-X)

B - Cl2

4FAo[1 X]

4CAo(1 X)(4.5)/(5-X)

C - HCl4

4FAoX

4CAoX(4.5)/(5-X)

D(g) - CCl4 (g)

0.1 FT

CAo(5-X)(4.5)/(5-X) = 0.5CAo

total

FAo(5-X)/0.9

CAo(5-X)(4.5)/(5-X) = 0.5CAo

specie